2026-04-13T00:57:32Zhttps://recercat.cat/oai/request

oai:recercat.cat:10256/113462024-06-18T13:49:25Zcom_2072_452955com_2072_2054col_2072_453073

2024-06-18T13:49:25Z urn:hdl:10256/11346 Intramolecular [2+2+2] cycloaddition reactions of Yne-ene-yne and Yne-yne-ene enediynes catalysed by Rh I: Experimental and theoretical mechanistic studies Dachs Soler, Anna Pla i Quintana, Anna Parella Coll, Teodor Solà i Puig, Miquel Roglans i Ribas, Anna Reaccions d'addició Addition reactions Funcional de densitat, Teoria del Density functionals Mecanismes de reacció (Química) Reaction mechanisms (Chemistry) Rodi Rhodium Ciclització (Química) Ring formation (Chemistry) N-Tosyl-linked open-chain yne-ene-yne enediynes 1 and 2 and yne-yne-ene enediynes 3 and 4 have been satisfactorily synthesised. The [2+2+2] cycloaddition process catalysed by the Wilkinson catalyst [RhCl(PPh 3) 3] was tested with the above-mentioned substrates resulting in the production of high yields of the cycloadducts. Enediynes 1 and 2 gave standard [2+2+2] cycloaddition reactions whereas enediynes 3 and 4 suffered β-hydride elimination followed by reductive elimination of the Wilkinson catalyst to give cycloadducts, which are isomers of those that would be obtained by standard [2+2+2] cycloaddition reactions. The different reactivities of these two types of enediyne have been rationalised by density functional theory calculations Financial support from the Spanish MICINN (CTQ2008-05409-C02-02, CTQ2008-03077, CTQ2011-23156, CTQ2011-23121 and CTQ2009-08328) and the Catalan DIUE of the Generalitat de Catalunya (2009SGR637) is acknowledged. A. D. thanks the Spanish MEC for a doctoral fellowship. Support for the research of M. S. was received through the ICREA Academia 2009 prize for excellence in research funded by the DIUE 2024-06-18T13:49:25Z 2024-06-18T13:49:25Z info:eu-repo/date/embargoEnd/2026-01-01 info:eu-repo/date/embargoEnd/2026-01-01 2011-12 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion http://hdl.handle.net/10256/11346 info:eu-repo/semantics/altIdentifier/doi/10.1002/chem.201102210 info:eu-repo/semantics/altIdentifier/issn/0947-6539 info:eu-repo/semantics/altIdentifier/eissn/1521-3765 info:eu-repo/grantAgreement/MICINN//CTQ2011-23121/ES/APLICACIONES CATALITICAS DE COMPUESTOS DE RODIO, PALADIO Y NIQUEL EN SINTESIS ORGANICA. METODOLOGIA Y ESTUDIOS MECANISTICOS./ info:eu-repo/grantAgreement/MICINN//CTQ2008-03077/ES/CLUSTERES METALICOS Y SEMIMETALICOS. ESTUDIOS DE AROMATICIDAD Y REACTIVIDAD/ info:eu-repo/grantAgreement/MICINN//CTQ2008-05409-C02-02/ES/SINTESIS, REACTIVIDAD Y APLICACIONES DE MACROCICLOS POLIINSATURADOS Y SUS PRECURSORES. ESTUDIOS MECANISTICOS MEDIANTE ESI-MS./ info:eu-repo/grantAgreement/MICINN//CTQ2011-23156/ES/AVANCES EN CATALISIS Y AROMATICIDAD/ AGAUR/2009-2014/2009 SGR-637 Tots els drets reservats info:eu-repo/semantics/embargoedAccess Wiley-VCH Verlag © Chemistry - A European Journal, 2011, vol. 17, núm. 51, p. 14493-14507 Articles publicats (D-Q)